Interstitial atoms in metal-metal bonded arrays: The synthesis and characterization of heptascandium decachlorodicarbide, Sc7Cl10C2, and comparison with the interstitial-free Sc7Cl10

Shiou Jyh Hwu, John D. Corbett, Kenneth R Poeppelmeier

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Abstract

Reaction of Sc strips, ScCl3, and graphite at 860-1000°C gives Sc7Cl10C2 in quantitative yields, with transport occurring at the higher temperatures; adventitious carbon will also produce the phase. The compound has been shown to be isostructural with Er7I10 by single-crystal X-ray diffraction (a=18.620 (4) Å, b=3.4975 (6) Å, c=11.810 (2) Å, β=99.81 (2)o; space group C2/m, Z=2, R=0.029, Rw=0.046 for 676 reflections, MoKα, 27Cl10, from which the heavy atom arrangement can be derived by displacement of all metal atoms by b/2 so as to convert chlorine functions on the metal chain from face-capping to edge-bridging. The driving force for this is thought to be the reduction of carbon-chlorine repulsive interactions. Core and valence XPS data for Sc7Cl10, Sc7Cl10Cl2, Sc2Cl2C, ScCl3, and Sc are presented to demonstrate the appearance of a carbide-like state for the interstitial, the presence of two different types of scandium in the first two comopounds, the oxidation of the chain that accompanies the carbon insertion, and a substantial Sc-C covalency. The latter arises through mixing of the interstitial's 2s and 2p valence orbitals with metal-metal bonding cluster orbitals of the same symmetry.

Original languageEnglish
Pages (from-to)43-58
Number of pages16
JournalJournal of Solid State Chemistry
Volume57
Issue number1
DOIs
Publication statusPublished - Mar 15 1985

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interstitials
Metals
Atoms
chlorine
Carbon
carbon
Chlorine
synthesis
metal-metal bonding
metals
valence
atoms
orbitals
scandium
Scandium
carbides
Graphite
insertion
strip
graphite

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Ceramics and Composites
  • Electronic, Optical and Magnetic Materials
  • Materials Chemistry
  • Condensed Matter Physics

Cite this

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title = "Interstitial atoms in metal-metal bonded arrays: The synthesis and characterization of heptascandium decachlorodicarbide, Sc7Cl10C2, and comparison with the interstitial-free Sc7Cl10",
abstract = "Reaction of Sc strips, ScCl3, and graphite at 860-1000°C gives Sc7Cl10C2 in quantitative yields, with transport occurring at the higher temperatures; adventitious carbon will also produce the phase. The compound has been shown to be isostructural with Er7I10 by single-crystal X-ray diffraction (a=18.620 (4) {\AA}, b=3.4975 (6) {\AA}, c=11.810 (2) {\AA}, β=99.81 (2)o; space group C2/m, Z=2, R=0.029, Rw=0.046 for 676 reflections, MoKα, 27Cl10, from which the heavy atom arrangement can be derived by displacement of all metal atoms by b/2 so as to convert chlorine functions on the metal chain from face-capping to edge-bridging. The driving force for this is thought to be the reduction of carbon-chlorine repulsive interactions. Core and valence XPS data for Sc7Cl10, Sc7Cl10Cl2, Sc2Cl2C, ScCl3, and Sc are presented to demonstrate the appearance of a carbide-like state for the interstitial, the presence of two different types of scandium in the first two comopounds, the oxidation of the chain that accompanies the carbon insertion, and a substantial Sc-C covalency. The latter arises through mixing of the interstitial's 2s and 2p valence orbitals with metal-metal bonding cluster orbitals of the same symmetry.",
author = "Hwu, {Shiou Jyh} and Corbett, {John D.} and Poeppelmeier, {Kenneth R}",
year = "1985",
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T1 - Interstitial atoms in metal-metal bonded arrays

T2 - The synthesis and characterization of heptascandium decachlorodicarbide, Sc7Cl10C2, and comparison with the interstitial-free Sc7Cl10

AU - Hwu, Shiou Jyh

AU - Corbett, John D.

AU - Poeppelmeier, Kenneth R

PY - 1985/3/15

Y1 - 1985/3/15

N2 - Reaction of Sc strips, ScCl3, and graphite at 860-1000°C gives Sc7Cl10C2 in quantitative yields, with transport occurring at the higher temperatures; adventitious carbon will also produce the phase. The compound has been shown to be isostructural with Er7I10 by single-crystal X-ray diffraction (a=18.620 (4) Å, b=3.4975 (6) Å, c=11.810 (2) Å, β=99.81 (2)o; space group C2/m, Z=2, R=0.029, Rw=0.046 for 676 reflections, MoKα, 27Cl10, from which the heavy atom arrangement can be derived by displacement of all metal atoms by b/2 so as to convert chlorine functions on the metal chain from face-capping to edge-bridging. The driving force for this is thought to be the reduction of carbon-chlorine repulsive interactions. Core and valence XPS data for Sc7Cl10, Sc7Cl10Cl2, Sc2Cl2C, ScCl3, and Sc are presented to demonstrate the appearance of a carbide-like state for the interstitial, the presence of two different types of scandium in the first two comopounds, the oxidation of the chain that accompanies the carbon insertion, and a substantial Sc-C covalency. The latter arises through mixing of the interstitial's 2s and 2p valence orbitals with metal-metal bonding cluster orbitals of the same symmetry.

AB - Reaction of Sc strips, ScCl3, and graphite at 860-1000°C gives Sc7Cl10C2 in quantitative yields, with transport occurring at the higher temperatures; adventitious carbon will also produce the phase. The compound has been shown to be isostructural with Er7I10 by single-crystal X-ray diffraction (a=18.620 (4) Å, b=3.4975 (6) Å, c=11.810 (2) Å, β=99.81 (2)o; space group C2/m, Z=2, R=0.029, Rw=0.046 for 676 reflections, MoKα, 27Cl10, from which the heavy atom arrangement can be derived by displacement of all metal atoms by b/2 so as to convert chlorine functions on the metal chain from face-capping to edge-bridging. The driving force for this is thought to be the reduction of carbon-chlorine repulsive interactions. Core and valence XPS data for Sc7Cl10, Sc7Cl10Cl2, Sc2Cl2C, ScCl3, and Sc are presented to demonstrate the appearance of a carbide-like state for the interstitial, the presence of two different types of scandium in the first two comopounds, the oxidation of the chain that accompanies the carbon insertion, and a substantial Sc-C covalency. The latter arises through mixing of the interstitial's 2s and 2p valence orbitals with metal-metal bonding cluster orbitals of the same symmetry.

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